Basic principles of organic chemistry

PREFACE v 1 INTRODUCTION. WHAT IS ORGANIC CHEMISTRY ALL ABOUT? 1 1-1 A Bit of History 1-2 What Preparation Should You Have? 1-3 Why Is Organic Chemistry Special? 1-4 The Breadth of Organic Chemistry 1-5 Some Philosophical Observations 2 STRUCTURAL ORGANIC CHEMISTRY. THE SHAPES OF MOLECULES. FUNCTIONAL GROUPS 30 2-1 Structural Formulas 30 2-2 The Sizes and Shapes of Organic Molecules. Molecular Models 34 2-3 Classification of Organic Compounds by Functional Groups 39 2-4 Isomerism in Organic Compounds 44 3 ORGANIC NOMENCLATURE 49 3-1 Alkanes 5 1 3-2 Cycloalkanes 57 3-3 Alkenes, Cycloalkenes, and Alkadienes 59 3-4 Alkynes 61 3-5 Arenes 62 4 ALKANES 69 4-1 Physical Properties of Alkanes. The Concept of Homology 70 4-2 Chemical Reactions of Alkanes. Combustion of Alkanes 73 4-3 Combustion. Heats of Reaction. Bond Energies 76 4-4 Halogenation of Alkanes. Energies and Rates of Reactions 8 1 4-5 Practical Halogenations. Problems of Selectivity 98 4-6 Nitration of Alkanes 105 5 STEREOISOMERISM OF ORGANIC MOLECULES 110 5- 1 Configurational Isomers 111 5-2 Conformational Isomers 12 1 5-3 Representation of Organic Structure 125 5-4 The D,L Convention for Designating Stereochemical Configurations 13 1 5-5 Molecules with More Than One Chiral Center. Diastereomers 133 5-6 Some Examples of the Importance of Stereoisomerism to Biology. Biological Stereospecificity 140 6 BONDING IN ORGANIC MOLECULES. ATOMIC-ORBITAL MODELS 150 6-1 Hydrogenlike Atomic Orbitals 15 1 6-2 Bond Formation Using Atomic Orbitals 155 6-3 Electron Repulsion and Bond Angles. Orbital Hybridization 157 6-4 Atomic-Orbital Models 162 6-5 Resonance 172 6-6 Advanced Quantum Theory of Organic Molecules 179 MORE ON NOMENCLATURE. COMPOUNDS OTHER THAN HYDROCARBONS 185 7-1 General Approaches to Naming Organic Compounds 7-2 Alcohols and Phenols: ROH, ArOH 7-3 Ethers, ROR' 7-4 Aldehydes, RCHO 7-5 Ketones, RCOR' 7-6 Carboxylic Acids, RC0,H 0 I I 7-7 Acyl Groups, R-C- 196 7-8 Amines: RNH,, R,NH, R,N 7-9 Nitriles, RCN 7-10 The Use of Greek Letters to Denote Substituent Positions 7- 1 1 Single- or Multiple-Word Names 8 NUCLEOPHILIC SUBSTITUTION AND ELIMINATION REACTIONS 8-1 Classification of Reagents as Electrophiles and Nucleophiles. Acids and Bases 8-2 Thermochemistry of Substitution Reactions 8-3 General Considerations of Substitution Reactions 8-4 Mechanisms of S, Reactions 8-5 Stereochemistry of SN2 Reactions 8-6 Stereochemistry of S,1 Reactions 8-7 Structural and Solvent Effects in SN Reactions Elimination Reactions 8-8 The E2 Reaction 8-9 The El Reaction SEPARATION AND PURIFICATION. IDENTIFICATION OF ORGANIC COMPOUNDS BY SPECTROSCOPIC TECHNIQUES 9-1 How Do We Know When an Organic Compound Is Pure? 9-2 Chromatographic Separation Procedures 9-3 Why Can't We See Molecules? Some General Considerations of Diffraction and Spectroscopic Techniques 9-4 Atomic Energy States and Line Spectra 9-5 Energy States of Molecules 9-6 Microwave Spectra. Rotational Spectra 9-7 Infrared Spectroscopy. Vibration-Rotation Spectra 9-8 Raman Spectroscopy 9-9 Electronic Spectra of Organic Molecules 9- 10 Nuclear Magnetic Resonance Spectroscopy 9- 1 1 Mass Spectroscopy ALKENES AND ALKYNES I. IONIC AND RADICAL ADDITION REACTIONS 10-1 Physical and Spectroscopic Properties of Alkenes and Alkynes 10-2 The Reactivity of Multiple Carbon-Carbon Bonds 10-3 Electrophilic Additions to Alkenes 10-4 Orientation in Addition to Alkenes 10-5 Electrophilic Addition Reactions of Alkynes 10-6 Nucleophilic Addition Reactions 10-7 Radical-Chain Addition Reactions to Alkenes 10-8 Polymerization of Alkenes 10-9 Alkylation of Alkenes 11 ALKENES AND ALKYNES II. OXIDATION AND REDUCTION REACTIONS. ACIDITY OR ALKYNES 1 1-1 Oxidation-Reduction of Organic Compounds 11-2 Hydrogenation with Heterogeneous Catalysts 11-3 Heats of Hydrogenation 11-4 Hydrogenation with Homogeneous Catalysts 11-5 Hydrogenation with Diimide 11-6 Addition of Boron Hydrides to Alkenes. Organoboranes 11-7 Oxidation Reactions 1 1-8 I-Alkynes as Acids CYCLOALKANES, CYCLOALKENES, AND CYCLOALKYNES 12-1 Nomenclature and Physical Properties of Cycloalkanes 12-2 Spectroscopic Properties of Cycloalkanes 12-3 Conformations of Cycloalkanes 12-4 Strain in Cycloalkane Rings 12-5 Chemical Properties 12-6 The Larger Cycloalkanes and Their Conformations 12-7 Cycloalkenes and Cycloalkynes 12-8 Nomenclature of Polycycloalkanes 12-9 Conformations of Decalin 12-10 Strain in Polycyclic Molecules POLYFUNCTIONAL COMPOUNDS. ALKADIENES. APPROACHES TO ORGANIC SYNTHESIS General Comments on Alkadienes 1,3- or Conjugated Dienes. Electrophilic and Radical Addition Cycloaddition Reactions Polymerization Reactions of Conjugated Dienes Cumulated Alkadienes Approaches to Planning Practical Organic Syntheses Building the Carbon Skeleton Introducing Functionality 13-9 Construction of Ring Systems by Cycloaddition Reactions 526 13- 10 Protecting Groups in Organic Synthesis 529 ORGANOHALOGEN AND ORGANOMETALLIC COMPOUNDS 14-1 Physical Properties 14-2 Spectroscopic Properties 14-3 Alkyl Halides 14-4 Alkenyl and Alkynyl Halides 14-5 Cycloalkyl Halides 14-6 Aryl Halides 14-7 Polyhalogenated Alkanes and Alkenes 14-8 Organometallic Compounds from Organohalogen Compounds 14-9 Properties of Organomatellic Compounds 14- 10 Preparation of Organometallic Compounds 14- 1 1 Organomagnesium Compounds 14-12 Organomagnesium and Organolithium Compounds in Synthesis 15- 1 Physical Properties of Alcohols; Hydrogen Bonding 15-2 Spectroscopic Properties of Alcohols 15-3 Preparation of Alcohols 15-4 Chemical Reactions of Alcohols. Reactions Involving the 0-H Bond 15-5 Reactions Involving the C-0 Bond of Alcohols 15-6 Oxidation of Alcohols 15-7 Polyhydric Alcohols 15-8 Unsaturated Alcohols - Alkenols 15-9 Protection of Hydroxyl Groups Ethers 15-10 Types and Reactions of Simple Ethers 15-1 1 Cyclic Ethers ' 16 CARBONYL COMPOUNDS I. ALDEHYDES AND KETONES. ADDITION REACTIONS OF THE CARBONYL GROUP 67 1 16-1 The Carbonyl Bond 16-2 Physical Properties 16-3 Spectroscopic Properties 16-4 Some Typical Carbonyl-Addition Reactions 16-5 Catalytic Hydrogenation 16-6 Reduction of Carbonyl Compounds to Hydrocarbons 16-7 Oxidation of Carbonyl Compounds 16-8 Protection of Carbonyl Groups 16-9 Preparative Methods for Aldehydes and Ketones CARBONYL COMPOUNDS II. ENOLS AND ENOLATE ANIONS. UNSATURATED AND POLYCARBONYL COMPOUNDS 17-1 Enolization of Aldehydes and Ketones 17-2 Halogenation of Aldehydes and Ketones 17-3 Nucleophilic Addition Reactions of Enolate Anions 17-4 Nucleophilic Substitution with Enolate Anions Unsaturated Carbonyl Compounds 17-5 a$-Unsaturated Aldehydes and Ketones 17-6 Ketenes Polycarbonyl Compounds 17-7 l,2-Dicarbonyl Compounds 17-8 1,3-Dicarbonyl Compounds 17-9 1,4-Dicarbonyl Compounds 17- 10 Tricarbonyl Compounds 17- 1 1 Cyclopropanones and Cyclopropenones 18 CARBOXYLIC ACIDS AND THEIR DERIVATIVES 18-1 Physical Properties of Carboxylic Acids 18-2 Some Chemical Properties of Carboxylic Acids 18-3 Reactions at the Carbonyl Carbon of Carboxylic Acids 18-4 Decarboxylation of Carboxylic Acids 18-5 Reactions at the Alpha Carbons of Carboxylic Acids 18-6 Functional Derivatives of Carboxylic Acids 18-7 Reactions at the Carbonyl Carbon of Acid Derivatives 18-8 Reactions at the Alpha Carbons of Carboxylic Acid Derivatives 18-9 Reactions of Unsaturated Carboxylic Acids and Their Derivatives 18- 10 Dicarboxylic Acids MORE ON STEREOCHEMISTRY 862 19-1 Plane-Polarized Light and the Origin of Optical Rotation 862 19-2 Specific Rotation 865 19-3 Separation or Resolution of Enantiomers 866 19-4 Enantiomeric Purity 870 19-5 Absolute and Relative Configuration 19-6 The R,S Convention for Designating Stereochemical Configurations 19-7 E,Z Notation 19-8 Prochirality 19-9 Optical Rotatory Dispersion. Circular Dichroism 19- 10 Asymmetric Synthesis 19- 1 1 Racemization 20 CARBOHYDRATES 20- 1 Classification and Occurrence of Carbohydrates 20-2 The Structure and Properties of D-Glucose 20-3 Conventions for Indicating Ring Size and Anomer Configurations of Monosaccharides 20-4 Derivatives of Glucose 20-5 Glycosides 20-6 Disaccharides 20-7 Polysaccharides 20-8 Vitamin C 20-9 Formation of Carbohydrates by Photosynthesis 20-10 The Generation of Energy from Carbohydrate Metabolism THE RESONANCE AND MOLECULAR-ORBITAL METHODS AND THEIR APPLICATIONS. PERlCYCLlC REACTIONS 2 1- 1 Characteristics of Simple Covalent Bonds 21-2 Comparison of the Resonance and Molecular-Orbital Methods 2 1-3 The Benzene Problem 21-4 Application of the MO Method to 1,3-Butadiene 21-5 Applications to Other Types of Systems 21-6 Which Treatment Is Better-MO or VB? 2 1-7 More on Stabilization Energies 21-8 Bond Lengths and Double-Bond Character 2 1-9 Hiickel's 4n + 2 Rule 2 1 - 10 Pericyclic Reactions 21-1 1 Evidence Bearing on the Mechanism of [2 + 21 Cycloadditions 22 ARENES. ELECTROPHILIC AROMATIC SUBSTITUTION 22- 1 Nomenclature 22-2 Physical Properties of Arenes xvi Contents 22-3 Spectral Properties of Arenes 22-4 Electrophilic Aromatic Substitution 22-5 Effect of Substituents on Reactivity and Orientation in Electrophilic Aromatic Substitution 22-6 Orientation in Disubstituted Benzenes 22-7 IPS0 Substitution 22-8 Substitution Reactions of Polynuclear Aromatic Hydrocarbons 22-9 Addition Reactions of Arenes 22- 10 Oxidation Reactions 22- 1 1 Sources and Uses of Aromatic Hydrocarbons 22-12 Some Conjugated Cyclic Polyenes 22- 13 Fluxional Compounds ORGANONITROGEN COMPOUNDS I. AMINES 23-1 Amines Compared with Alcohols 23-2 Some Naturally Occurring Amines. Alkaloids and Related Compounds 23-3 Types and Nomenclature of Amines 23-4 Physical Properties of Amines 23-5 Spectroscopic Properties of Amines 23-6 Stereochemistry of Amines 23-7 Amines as Bases 23-8 Amines as Acids 23-9 Amines as Nucleophiles 23- 10 Amines with Nitrous Acid 23- 1 1 Oxidation of Amines 23-12 Synthesis of Amines 23-13 Protection of Amino Groups in Synthesis 23- 14 Carcinogenic Nitrogen Compounds 24 ORGANONITROGEN COMPOUNDS II. AMIDES, NITRILES, NITRO COMPOUNDS, AND SOME SUBSTANCES WITH N-N BONDS 1167 24-1 Structural, Physical, and Spectral Characteristics of Amides 1167 24-2 Amides as Acids and Bases 1175 24-3 Synthesis of Amides 1176 24-4 Hydrolysis of Amides 1182 24-5 Nitriles 1184 24-6 Nitro Compounds 1186 24-7 Some Compounds with N-N Bonds 1197 25 AMINO ACID, PEPTIDES, PROTEINS, ENZYMES, AND NUCLEIC ACIDS 1206 25-1 Types of Biologically Important Amino Acids 25-2 The Acid-Base Properties of a-Amino Acids 25-3 Physical and Spectroscopic Properties 25-4 Analysis of Amino Acids 25-5 Reactions of Amino Acids 25-6 Synthesis of a-Amino Acids 25-7 Peptides and Proteins 25-8 Structure and Function of Proteins 25-9 Enzymes 25- 10 Coenzymes 25-1 1 Enzyme Regulation 25- 12 Enzyme Technology 25-13 Biosynthesis of Proteins 25- 14 Chemical Evolution MORE ON AROMATIC COMPOUNDS. ARYL OXYGEN COMPOUNDS; SIDE-CHAIN DERIVATIVES 1287 26-1 Aryl Oxygen Compounds 26-2 Quinones 26-3 Tropolones and Related Compounds 26-4 Some Aromatic Side-Chain Compounds 26-5 Natural Occurrence and Uses of Some Aromatic Side-Chain Compounds 26-6 correlations of Structure with Reactivity of Aromatic Compounds MORE ABOUT SPECTROSCOPY. IMPORTANT, LESS-COMMON SPECTROSCOPIC METHODS 1342 27-1 How Can We Understand Line-Width Differences in NMR Spectroscopy? The Uncertainty Principle 1343 27-2 Use of the Uncertainty Principle to Measure the Rates of Chemical Transformations 1345 27-3 Why Spin-Spin Splitting? 1348 27-4 Chemically Induced Dynamic Nuclear Polarization (CIDNP) 1353 27-5 Photoelectron Spectroscopy 1356 xviii Contents 27-6 Mossbauer Spectroscopy 1359 27-7 Field- and Chemical-Ionization Mass Spectroscopy 1360 27-8 Ion-Cyclotron Resonance 1364 27-9 Electron-Spin Resonance (ESR) Spectroscopy of Organic Radicals 1366 28 PHOTOCHEMISTRY 1371 28-1 Light Absorption, Flourescence, and Phosphorescence 1372 28-2 Organic Photochemistry 1378 28-3 Chemiluminescence 1395 28-4 Color and Constitution 1399 28-5 The Sensation of Color 1409 28-6 Color Photography 1410 28-7 Chemistry of Vision 1416 29 POLYMERS 1419 29-1 A Simple Addition Polymerization. The Parts of a Polymer 1420 29-2 Types of Polymers 142 1 Physical Propert~eso f Polymers 1425 29-3 Forces Between Polymer Chains 1425 29-4 correlation of Polymer Properties with Structure 1430 Preparat~ono f Synthet~cP olymers 1437 29-5 Condensation Polymers 1438 29-6 Addition Polymers 1446 29-7 Block, Graft, and Ladder Polymers 1454 29-8 Naturally Occurring Polymers 1457 30 NATURAL PRODUCTS. BIOSYNTHESIS 1460 30-1 Classification of Natural Products 30-2 Approaches to the Study of Natural Products 30-3 Isoprenoid Compounds 30-4 Steroids 30-5 Biosynthesis 30-6 Some Nitrogen-Containing Natural Products 30-7 Prostaglandins TRANSITION-METAL ORGANIC COMPOUNDS 1504 3 1- 1 Metallocenes 1505 3 1-2 Other Organometallic Compounds of Transition Metals 1509 3 1-3 Transition-Metal Compounds as Reagents for Organic Syntheses 1512 3 1-4 Some Homogeneous Catalytic Reactions Involving Transition-Metal Complexes 1517 3 1-5 T-Propenyl Complexes of Nickel 1521 31-6 Vitamin B,, as an Organometallic Compound 1525 INDEX 1529